Our invention is directed to a process and electronic data processing software program for carrying out same, for the creation of flavor or fragrance formulations or for the determination of the use of a flavor or fragrance ingredient in a flavor or fragrance formulation or a use thereof in or on a perfume composition, perfumed article, cologne, foodstuff, beverage, oral care composition and/or chewing gum where the flavor or fragrance formulation or ingredient have a particular and desired solubility in a solvent such as water.
The process is carried out using apparatus which is a laser light beam transmitter fitted with a light scattering means and having attached thereto titration means.
The use of automatic titrators for the investigation of such protocols such as water treatment protocols concerning ascertaining how zeta potential changes with the addition of charged salts can improve flocculation procedures is disclosed in the brochure entitled THE ZETASIZER RANGE AUTOMATED DISPERSION TECHNOLOGY SOLUTIONS, published by Malvern Instruments Inc. of 10 Southville Road, Southborough, Mass. 01772. Furthermore, a brochure entitled DynaPro Dynamic Light Scattering Results Summary, published by Protein Solutions discloses the theory overview and data implementation of dynamic light scattering apparatus whereby monochromatic laser light passes through a solution of non-interacting molecules and the fluctuation and scattered intensity caused by molecules or particles moving in Brownian motion is measured. The speed at which the molecules move is indicated to be inversely related to their size, and it is disclosed in the Protein Solutions publication that the parameter measured is known as the Translational Diffusion Coefficient (Dt) whereby the apparent Hydrodynamic Radius (Rh) of the particles can then be calculated with known temperature and solvent viscosity. The scattered light passes through a photo detector and photon correlator and computer equipped with electronic data processing software for ascertaining particle size.
Nothing is set forth in the Protein Solutions brochure or in the Malvern Instruments brochure disclosing a process for the creation of a fragrance or flavor formulation or ascertainment of the use of a fragrance or flavor ingredient in a fragrance or flavor formulation or a use thereof in a fragrance composition, perfumed article, cologne, foodstuff, beverage, oral care composition or chewing gum, wherein the flavor or fragrance ingredient or flavor or fragrance formulation has predicted solvent solubility.
It is well known that a need exists for the ability to create, on an industrial scale, flavor or fragrance compositions which have a defined and predictable solubility in a solvent such as water so that such flavor or fragrance formulations can be utilized in aqueous compositions or in aqueous systems such as liquid fabric softener compositions, liquid detergent compositions, detergents which are powdered which come in contact with large amounts of water such as in washing machines, powdered fabric softeners or fabric softener tablets which come in contact with large amounts of water during the washing machine procedure and the like.
Nothing in the prior art, however, discloses a technique for fulfillment of the above-stated need.
Our invention sets forth a process and electronic data processing software program for carrying out same, for the creation of a flavor or fragrance formulation or for the determination of the use of a fragrance or flavor ingredient in a fragrance or flavor formulation or use thereof in or on a perfume composition, perfumed article, cologne, perfumed polymer, foodstuff, beverage, oral care product (e.g., mouthwash or toothpaste) and/or chewing gum.
The process of our invention effects the determination of solvent solubility of such materials thereby enabling the use of such materials in solvent (e.g., water) systems.
Such water systems are affiliated with washing procedures such as those carried out in the process of washing fabrics and the like.
The process of our invention uses, inter alia, apparatus which is a laser light beam transmitter fitted with a light scattering means, for example, the DynaPro-LSR Molecular Sizing Instrument manufactured by Protein Solutions, Inc. of 1224 West Main Street, Suite #777, Charlottesville, Va. 22903. In carrying out the process of our invention, such laser light beam transmitter fitted with light scattering means has attached thereto a titration means consisting of two burettes:
(a) a xe2x80x9csamplexe2x80x9d burette holding one or more flavor or fragrance ingredients or a fragrance or flavor formulation; and
(b) a xe2x80x9ctitrantxe2x80x9d burette holding a solvent such as water.
The burettes may also contain gelatin and/or a surfactant such as didecylammonium chloride.
The purpose of the surfactant is for the formation of micelles containing flavor or fragrance or flavor formulation or fragrance formulation. The use of the gelatin is to form encapsulated flavor or fragrance oils or flavor formulation or fragrance formulation oils which are encapsulated with a hard gelatin shell formed by means of coacervation as a result of the gelatin precipitating around globules of flavor or fragrance or flavor formulation or fragrance formulation oil formed at the xe2x80x9cendpointxe2x80x9d of the titration.
In general the surfactant useful in the practice of our invention are of the formula: 
wherein R1 and R2 are the same or different C5-C20 alkyl, alkenyl, alkadienyl aryalkyl, alkarylalkyl, aryalalkyl and alkatrienyl for example, n-decyl, n-undecyl phenylethyl, phenylpropyl and o-ethylphenyl n-propyl. More specifically, a preferred surfactant is the dicecylammonium chloride having the structure: 
In the foregoing generic structure, to wit: 
X represents halogen, e.g., chloro, bromo or iodo; or X represents hydroxyl.
The solvent and fragrance or flavor ingredient or flavor or fragrance formulations are automatically titrated into the light scattering means where a dynamic titrant/sample mixture is formed proximate a monitoring device. When using gelatin, coacervation of the gelatin around the fragrance or flavor microdroplet takes place first forming microcapsules and then enlarging same during the titration procedure. The formation of the microdroplets takes place during the titration at the xe2x80x9cendpointxe2x80x9d when the single phase liquid mixture reaches a point where the phases separate and microdroplets of flavor or fragrance ingredient or flavor or fragrance formulation form. At this xe2x80x9cendpoint,xe2x80x9d very shortly after formation of the microdroplets, coacervation of the gelatin contained in the solution occurs whereby the gelatin comes out of solution and coacervates around the microdroplets.
When using a surfactant, fragrance micelles are first formed and are then enlarged at the endpoint. The micelles, which are formed, are formed as a result of the presence of surfactant at the endpoint of the titration. At the end point of the titration when the micelles are formed, microdroplets of flavor or fragrance ingredient or flavor or fragrance formulation are first formed followed by formation of the micelles.
Thus, the titration proceeds to a detectable endpoint where (i) single aqueous phase converts to a two phase particle/liquid phase system, e.g., a colloidal suspension or (ii) fragrance and flavor ingredient or flavor and fragrance formulation micelles or microcapsules are formed in the system and then enlarged.
Monitoring for the endpoint appearance, using specially designed electronic data processing software as set forth in detail, infra, will yield information concerning particle dimensions (e.g., hydration diameter) and will then yield water solubility data using derived algorithms, also as described in detail, infra.
More specifically, our invention provides a process for the creation of a fragrance or flavor formulation or ascertainment of the use of a flavor or fragrance ingredient in a fragrance formulation or use thereof on or in a foodstuff, beverage, chewing gum or oral care formulation or in a perfumed article, perfume composition, cologne, perfumed polymer or fragrance composition having predictable solvent solubility (for example, water solubility), comprising the steps of:
(i) providing a laser light beam transmitter fitted with a laser light scattering means;
(ii) providing a titration means upstream from and cooperating with said laser light scattering means consisting of two injection means (e.g., burettes), a first xe2x80x9ctitrantxe2x80x9d injection means containing a solvent (e.g., water) and a second xe2x80x9csamplexe2x80x9d injection means containing a flavor or fragrance formulation or flavor or fragrance ingredient, with each of said injection means being connected to fluid transmission means (e.g., tubes) for transmitting and mixing said titrant with said sample in order to create a xe2x80x9cdynamic titrant/sample mixture in the liquid phasexe2x80x9d;
(iii) continuously transporting said dynamic/titrant sample mixture through said laser light scattering means while substantially simultaneously (a) titrating said dynamic/titrant sample mixture to a solvent solubility endpoint and (b) monitoring said dynamic/titrant sample mixture in order to ascertain the dimensions of particles or globules formed or enlarged while said dynamic/titrant sample mixture is being transported within said laser light scattering means.
The foregoing process can also utilize a mixture in the sample means of surfactant and fragrance or flavor ingredient or flavor or fragrance formulation; and in the titrant means, water. In such a situation, the endpoint is represented by the formation of micelles and the enlargement of such micelles.
In monitoring the micelles when in contact with water, an enlargement of the micelles will be quantitatively a function of the solubility of the flavor ingredient or the fragrance ingredient or the flavor formulation or the fragrance formulation in the solvent, for example, water. Such a relationship between the solubility in water of the xe2x80x9csamplexe2x80x9d and the degree of enlargement of the microparticle, e.g., the micelle in this case, is governed according to the algorithm:       F    SAT    =                              k          2                                      k            1                    ⁢                      xe2x80x83                    ⁢                      k            3                              ⁢              xe2x80x83            ⁢                        e                                    k              2                        ⁢                          xe2x80x83                        ⁢            θ                          ⁡                  [                                    ∂              W                                      ∂              θ                                ]                      -          4      ⁢              xe2x80x83            ⁢      π      ⁢              xe2x80x83            ⁢                        R          2                ⁡                  [                                    ∂              R                                      ∂              θ                                ]                    
wherein k1, k2 and k3 are constants; wherein the symbol xcex8 is representative of time; wherein R is globule radius; wherein the term   [            ∂      R              ∂      θ        ]
represents the rate of change of the radius of the globule or microparticle with respect to time; wherein the term   [            ∂      W              ∂      θ        ]
represents the rate of water entry into the globule with respect to time or the rate of solvent entry into the globule or microparticle with respect to time; and wherein the term FSAT represents the saturation level for the xe2x80x9csamplexe2x80x9d that is, for the fragrance ingredient or flavor ingredient or fragrance formulation or flavor formulation previously located in the sample means.
The foregoing algorithm is used in conjunction with the following algorithm:       g    ⁢          xe2x80x83        ⁢          (      θ      )        =      p    ⁢          xe2x80x83        ⁢          (      Γ      )        ⁢          xe2x80x83        ⁢          {                                                  e                              (                                                      -                                          2                      3                                                        ⁢                                      xe2x80x83                                    ⁢                                                            KT                      ⁢                                              xe2x80x83                                            ⁢                                              θ                        ⁡                                                  [                                                      8                            ⁢                                                          xe2x80x83                                                        ⁢                            π                            ⁢                                                          xe2x80x83                                                        ⁢                                                          n                              2                                                        ⁢                                                          xe2x80x83                                                        ⁢                                                                                          sin                                2                                                            ⁡                                                              [                                                                  α                                  2                                                                ]                                                                                                              ]                                                                                                            3                      ⁢                                              xe2x80x83                                            ⁢                      η                      ⁢                                              xe2x80x83                                            ⁢                      R                      ⁢                                              xe2x80x83                                            ⁢                                              λ                        2                                                                                            )                                                                                        xe2x80x83                                          }      
wherein the term g(xcex8) represents the normalized intensity correlation function; the symbol xcex represents the scattered light wave length; the symbol xcex1 represents the scattering angle; the symbol xcex7 represents the solvent viscosity; the symbol T represents temperature (absolute degrees Kelvin); n is the refractive index of the sample, that is the fragrance ingredient or flavor ingredient or the fragrance formulation or the flavor formulation; K is the Boltzmann constant.
The aforementioned algorithm is derived from the following algorithms:                     g        ⁢                  xe2x80x83                ⁢                  (          θ          )                    =                                    [                          p              ⁢                              xe2x80x83                            ⁢                              (                Γ                )                                      ]                    ⁢                      xe2x80x83                    ⁢                      e                                          -                2                            ⁢                              xe2x80x83                            ⁢              Γ              ⁢                              xe2x80x83                            ⁢              θ                                      +        1              ;          xe2x80x83        ⁢          Γ      =                        D          T                ⁢                  xe2x80x83                ⁢                  q          2                      ;          xe2x80x83        ⁢          q      =                                    4            ⁢                          xe2x80x83                        ⁢            π            ⁢                          xe2x80x83                        ⁢            n                    λ                ⁢                  xe2x80x83                ⁢        sin        ⁢                  xe2x80x83                ⁢                  (                      α            2                    )                      ;    and              D      T        =                  KT                  6          ⁢                      xe2x80x83                    ⁢          π          ⁢                      xe2x80x83                    ⁢          η          ⁢                      xe2x80x83                    ⁢          R                    .      
wherein q is the scattering vector for the scattered light and DT is the translation diffusion coefficient.
In another embodiment of our invention, the titrant is a mixture of water and gelatin and the sample is a flavor or fragrance ingredient or a flavor or fragrance formulation; and the endpoint is represented by formation and enlargement of a coacervation wherein enlarged gelatin microcapsules containing fragrance ingredient or flavor ingredient or fragrance formulation or flavor formulation are formed.
The microcapsules initially have a radius R and on continued immersion in a solvent such as water, fragrance or flavor is evolved from the microcapsule into the solvent and, simultaneously, solvent, e.g., water, enters via osmosis each of the microcapsules causing the microcapsules to swell and causing the radius R to expand by an increment, xcex94R, whereby the final radius is shown by the term R=R0+xcex94R and wherein the increase of radius is also shown by the equation:       Δ    ⁢          xe2x80x83        ⁢    R    =            ∫      0      θ        ⁢                  (                              ∂            R                                ∂            θ                          )            ⁢              xe2x80x83            ⁢                        ⅆ          θ                .            
The process of our invention also includes the additional step of using the solubility data generated from endpoint particle size or globule size data ascertained using the aforementioned algorithms to ascertain solvent-soluble fragrance ingredient or formulation or solvent-soluble flavor ingredient or formulation and then crafting said formulation utilizing the data.
The resulting formulations may then be added to colognes, perfumed polymers and perfumed articles (in the case of fragrance ingredients or fragrance formulations) or to foodstuffs, chewing gums, beverages or oral care products (in the case of fragrance ingredients or flavor formulations). Perfumed articles include but are not limited to solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, fabric softener articles and hair care preparations including shampoos and bleach formulations.
In crafting the electronic data processing program software, the following steps are utilized in the practice of our invention:
1(a). ascertaining the nature of the light scattering material to be formed at the endpoint, e.g., microcapsule or micelle;
1(b). input of the data of 1(a) into memory;
2(a). establishment of the use of the ultimate flavor ingredient or flavor formulation or fragrance ingredient or fragrance formulation;
(2(b). input of the data of 2(a) into memory;
3(a). establishment of constraints for:
(i) flavor or fragrance ingredient or formulation aroma profile;
(ii) fragrance or flavor ingredient or formulation profile on treated product (e.g., perfumed article); and
(iii) total fragrance or flavor ingredient or formulation solvent solubility (e.g., water solubility);
3(b). input of constraints of 3(a) into memory;
4. effecting loading of titrant burette or syringe with solvent (e.g., water) and, optionally, coacervating material in given proportion to solvent;
5. effecting loading of sample syringe or burette with sample (e.g., fragrance ingredient or flavor ingredient or fragrance or flavor formulation) (and, optionally, in set proportions, surfactant and/or coacervating material);
6(a). setting system to reject solvent (e.g., water) solubility of sample (e.g., flavor or fragrance ingredient or formulation) below SA, e.g., to wit: xe2x80x9creject if Sixe2x89xa6SAxe2x80x9d and xe2x80x9caccept if Si greater than SAxe2x80x9d;
6(b). input data of 6(a) into memory;
7. engage light scattering apparatus;
8(a). simultaneously engage sample syringe or burette at rate xcfx81S and titrant injection burette at rate xcfx81T through microsampler whereby endpoint may be reached and ascertained causing solubility in solvent to be ascertained via automatic calculation using algorithms and indicating fragrance or flavor ingredient or formulation saturation level in solvent and relationship of such saturation level to globule or particle size or capsule or micelle size;
8(b). entry of output of 8(a) into memory;
9. is Si greater than SA, if so accept;
10. repeat steps 4 and 5, k times at   k  2
xe2x80x83different rates of xcfx81S; and   k  2
xe2x80x83different rates of xcfx81T; and   k  3
xe2x80x83different ratios of xcfx81S:xcfx81T and   k  3
xe2x80x83different temperatures in order to develop means for FSAT of given temperatures; and for each repetition, repeat steps 6(a) and 6(b);
11. plot data for steps 5, 6(a), 10 and 11 and input to memory;
12. repeat steps 1-11 for m fragrance or flavor ingredients and formulations, [F1F2, . . . Fmxe2x88x921,Fm] wherein m is an integer of from 4 up to 100;
13. scan accepted data and formulate entire flavor and fragrance formulations based on data; and add to sample burettes for solubility determination. Set to accept if [xcexa3Si] greater than SB and set to reject if [xcexa3Si]xe2x89xa6SB where S represents solubilities and SA and SB represent target solubilities with Si representing sample solubilities. [In each of the foregoing xe2x80x9cacceptancexe2x80x9d or xe2x80x9crejectionxe2x80x9d cases, prior to such acceptance or rejection, there is still a rejection if the endpoint is such that the fraction of samples and titrants committed are less than about 0.2, e.g., f less than 0.2 and acceptance if the fractions of sample and titrant are greater than or equal to 0.2, to wit, fxe2x89xa70.2.]
[The formulations are carried out desirably at a xe2x80x9cperfumer""s workstation,xe2x80x9d xe2x80x9cPWS.xe2x80x9d]
If the resultant materials are rejected from the perfumer""s workstation, at this point the flavor or fragrance formulation is reworked and steps 1-7 are repeated; and
14. apply the resultant formulation to a substrate, e.g., perfumed article, such as a solid or liquid anionic, cationic, nonionic or zwitterionic detergent. The resultant product is either accepted or rejected based upon the aroma thereof as evaluated instantaneously and over a period of time. If, at this point, the sample is rejected, then the sample is reworked by repeating therefor steps 1-7.